Imprints of hydrocarbon-bearing basinal fluids on a karst system: mineralogical and fluid inclusion studies from the Buda Hills,Hungary

Calcite veins and related sulphate–sulphide mineralisation are common in the Buda Hills. Also, abundant hypogenic caves are found along fractures filled with these minerals pointing to the fact that young cave-forming fluids migrated along the same fractures as the older mineralising fluids did. The studied vein-filling paragenesis consists of calcite, barite, fluorite and sulphides. The strike of fractures is consistent—NNW–SSE—concluding a latest Early Miocene maximum age for the formation of fracture-filling minerals. Calcite crystals contain coeval primary, hydrocarbon-bearing- and aqueous inclusions indicating that also hydrocarbons have migrated together with the mineralising fluids. Hydrocarbon inclusions are described here for the first time from the Buda Hills. Mixed inclusions, i.e., petroleum with ‘water-tail’, were also detected, indicating that transcrystalline water migration took place. The coexistence of aqueous and petroleum inclusions permitted to establish the entrapment temperature (80°C) and pressure (85 bar) of the fluid and thus also the thickness of sediments, having been eroded since latest Early Miocene times, was calculated (800 m). Low salinity of the fluids (<1.7 NaCl eq. wt%) implies that hydrocarbon-bearing fluids were diluted by regional karst water. FT-IR investigations revealed that CO₂ and CH₄ are associated with hydrocarbons. Groundwater also contains small amounts of HC and related gases on the basin side even today. Based on the location of the paleo- and recent hydrocarbon indications, identical migration pathways were reconstructed for both systems. Hydrocarbon-bearing fluids are supposed to have migrated north-westward from the basin east to the Buda Hills from the Miocene on.     

Rockfalls detached from a lateral moraine during spring season. 2010 and 2011 events observed at the Rebaixader debris-flow monitoring site (Central Pyrenees, Spain)

Instability processes at glacial deposits represent an important hazard in mountainous areas. During the spring seasons of 2010 and 2011, two falls of large boulders (18 and 55? m³) initiated in a lateral moraine in the Rebaixader catchment (Central Pyrenees, Spain). Detailed information was gathered due to the debris-flow monitoring system installed along the torrent. Meteorological data showed that the two rockfalls were triggered without important rainfall amounts. Field surveys, ground vibration acquired at geophones and the movie recorded with a video camera provided unique information on the rockfall occurrence and dynamics. In addition, the information gave an excellent opportunity to show the importance of monitored data for the calibration of model parameters for runout simulations. The analysis focussed on the 2011 event and showed that the boulder passed rolling and bouncing through the monitored torrent reach. The velocity estimates in this reach range from 3 to 9 ?m/s. The 2011 rockfall was also back-analysed by a two-dimensional physically based model, which was fitted by the monitored and field data. The results of the simulation coincided well with recorded measurements, although the output could be improved by the application of a three-dimensional model.     

Lithosphere thermal structure at the eastern margin of the Bohemian Massif: a case petrological and geophysical study of the Nied?wied? amphibolite massif (SW Poland)

The crustal section beneath amphibolite Nied?wied? Massif (Fore-Sudetic Block in NE Bohemian Massif), modelled on the basis of geological and seismic data, is dominated by gneisses with subordinate granites (upper and middle crust) and melagabbros (lower crust). The geotherm was calculated based on the chemical analyses of the heat-producing elements in the rocks forming the crust and the measurements of their density and heat conductivity. The results were verified by heat flow calculations based on temperature measurements from 1,600?m deep well in the Nied?wied? Massif and by temperature–depth estimates in mantle xenoliths coming from the nearby ca. 4.5?My basanite plug in Lutynia. The paleoclimate-corrected heat flow in the Nied?wied? Massif is 69.5?mW?m^?2, and the mantle heat flow is 28?mW?m^?2. The mantle beneath the Massif was located marginally relative to the areas of intense Cenozoic thermal rejuvenation connected with alkaline volcanism. This results in geotherm which is representative for lithosphere parts located at the margins of zones of continental alkaline volcanism and at its waning stages. The lithosphere–asthenosphere boundary (LAB) beneath Nied?wied? is located between 90 and 100?km depth and supposedly the rheological change at LAB is not related to the appearance of melt.     

Generation and emplacement of shear-related highly mobile crustal melts: the synkinematic leucogranites from the Variscan Tormes Dome, Western Spain

The Tormes dome consists of S-type granites that intruded into Ordovician augen gneisses and Neoproterozoic–Lower Cambrian metapelites/metagreywackes at different extents of migmatization. S-type granites are mainly equigranular two-mica granites, occurring as: (1) enclave-laden subvertical feeder dykes, (2) small external sill-like bodies with size and shape relations indicative for self-similar pluton growth, and (3) as large pluton bodies, emplaced at higher levels than the external ones. These magmas were highly mobile as it is inferred from the high contents of fluxing components, the disintegration and alignment of pelitic xenoliths in feeder dykes and at the bottom of some sill-like bodies. Field relations relate this 311?Ma magmatism (U–Pb monazite) to the regional shearing of the D₃ Variscan event. Partial melting modeling and the relatively high estimated liquidus temperatures indicate biotite-dehydration partial melting (800–840°C and 400–650?MPa) rather than water-fluxed melting, implying that there was no partial melting triggered by externally derived fluids in the shear zones. Instead, the subvertical shear zones favored extraction of melts that formed during the regional migmatization event around 320?Ma. Nd isotope variation among the granites might reflect disequilibrium partial melting or different protoliths. Mass-balance and trace element partial melting modeling strongly suggest two kinds of fertile crustal protoliths: augen gneisses and metapelites. Slight compositional variation among the leucogranites does not reflect different extent of protolith melting but is related to a small amount of fractional crystallization (<13% for the equigranular granites), which is generally more pronounced in shallower batholitic leucogranites than in the small and homogeneous sill-like bodies. The lower extent of fractional crystallization and the higher-pressure emplacement conditions of the sill-like bodies support a more restricted movement through the crust than for batholitic leucogranites.     

Determination of Fluoride Ions in Iron Ores by UV–VIS Spectrophotometry after Matrix Removal Using Diphonix® Resin

A modification of the spectrophotometric method for the determination of fluoride ions in iron‐rich materials is proposed. In this method the iron matrix was successfully removed using Diphonix^® resin. The studied sample was a ferruginous mineral which contained about 38% of iron. The Euronorm certified reference material (ECRM) 676‐1 (Iron Ore Sinter), as a commercially available material having a similar matrix (39.76% w/w Fe) and fluoride level (0.1% w/w), was used to validate the method. After partial digestion in concentrated hydrochloric acid the samples were diluted and passed through Diphonix^® resin. The concentration of fluoride ions was determined by a spectrophotometric method using a Zr:ER complex (λ = 540 nm). The result obtained for the ECRM was in good agreement with the certificate specification and thus proved the method to be applicable for the determination of fluoride ions in iron‐rich materials. Due to the easy digestion step and simple requirements for equipment, this method can be used in most laboratories.     

The environmental impact of Aguilar mine on the heavy metal concentrations of the Yacoraite River,Jujuy Province,NW Argentina

The Yacoraite River and its tributaries run down the eastern slope of the Aguilar Range. It is one of the tributaries of the Rio Grande, located in Quebrada de Humahuaca, a UNESCO World Heritage site. The Aguilar underground mine (Pb–Ag–Zn) is located in the upper reaches of the Yacoraite River drainage basin. The aim of this work is to characterize the presence of heavy metals in water and sediments of the Yacoraite River and to identify their sources. The analysis shows the seasonal variation of heavy metals concentration in water and their relation with the World Health Organization (WHO) limits established for human consumption. The Yacoraite basin is naturally anomalous in some metals and some elements, such as As which is controlled by the chemical composition of regional lithology. During the wet season, Al, Co, Mo and Pb concentrations in water samples are higher than during the dry season; in addition, these metals are also higher than WHO limit values. High enrichment factors for Ba, Mo, Pb, Zn and Cd were found in Casa Grande stream, indicating the direct influence of the mining activities. Cd, Pb and Zn are present in the Aguilar ore minerals, such as sphalerite and galena. Sediments collected during the dry season show a drastic increase in the concentration of As, Pb, Ba, Zn, Cd and Mn. The Müller geo-accumulation index in Casa Grande indicates that it is a highly polluted stream. The concentrations of As, Pb, Ba, Zn, Cd are also high in Yacoraite River: Security Quality Guidelines indicates toxicity. A decrease in enrichment factors and geo-accumulation indices observed in sediments indicates the occurrence of precipitation/adsorption processes in the river to restore the equilibrium composition. Strict environmental controls in Aguilar Mine are necessary to avoid the uncontrolled input of toxic metals in Casa Grande stream and Yacoraite River.     

An approach for valid covariance estimation via the Fourier series

The use of kriging for construction of prediction or risk maps requires estimating the dependence structure of the random process, which can be addressed through the approximation of the covariance function. The nonparametric estimators used for the latter aim are not necessarily valid to solve the kriging system, since the positive-definiteness condition of the covariance estimator typically fails. The usage of a parametric covariance instead may be attractive at first because of its simplicity, although it may be affected by misspecification. An alternative is suggested in this paper to obtain a valid covariance from a nonparametric estimator through the Fourier series tool, which involves two issues: estimation of the Fourier coefficients and selection of the truncation point to determine the number of terms in the Fourier expansion. Numerical studies for simulated data have been conducted to illustrate the performance of this approach. In addition, an application to a real environmental data set is included, related to the presence of nitrate in groundwater in Beja District (Portugal), so that pollution maps of the region are generated by solving the kriging equations with the use of the Fourier series estimates of the covariance.     

Partition of arsenic in soils sediments and the origin of naturally elevated concentrations in groundwater of the southern pampa region (Argentina)

Excessive arsenic concentrations above the Argentinean and WHO guidelines for drinking water (10 μg L⁻¹) affects shallow aquifers of the southern Pampean Plain (Argentina) hosted in the Pampean and the Post Pampean formations (loess and reworked loess; Plio-Pleistocene–Holocene). Health problems related to high As concentrations in drinking waters are known as Endemic Regional Chronic Hydroarsenicism. Hydrochemistry of shallow groundwaters and soil geochemistry were investigated aiming to (1) understand the partition of As in the solid phase and its relationship with unacceptable As concentrations in waters, (2) identify the provision source of As to groundwaters. Only 5% of the samples had As concentrations <10 μg L⁻¹; in 27% As concentrations ranged from 10 to 50 μg L⁻¹ and in 58% it reached 60–500 μg L⁻¹. The coarse fraction (50–2,000 μm) hosts about 27% of the total As in the solid phase, being positively correlated to Ba (p < 0.01; r ² = 0.93). About 70% is included in the <2 μm fraction and had positive correlations of As–Fe (p < 0.05; r ² = 0.85) and As–Cr (p < 0.05; r ² = 0.68). Soils and sediment sand fractions of vadose zones are the primary sources of As in shallow groundwater while adsorption–desorption processes, codisolution–coprecipitation, and evaporation during the dry seasons raise As concentrations in waters exceeding the guideline value for drinking water.